Ultrasonic solvent extraction of organochlorine pesticides from soil

Ali Tor, Mehmet Emin Aydin , Senar Ozcan

Selcuk University, Department of Environmental Engineering, 42031 Campus, Konya, Turkey Received 8 September 2005; received in revised form 22 November 2005; accepted 25 November 2005 Available online 6 January 2006

Abstract Ultrasonic solvent extraction of the organochlorine pesticides (OCP) including -, -, - and -hexachlorocyclohexane (HCH), heptachlor, aldrin, o,p -DDE, dieldrin, p,p -DDE, p,p -DDT, methoxychlor, mirex from soil is reported. The extraction procedure was optimized with regard to the solvent type, amount of solvent, duration of sonication and number of extraction steps. Determination of pesticides was carried out by gas chromatography (GC) equipped with electron capture detection (ECD). Twice ultrasonic extraction using 25 mL of a mixture of petroleum ether and acetone (1/1 v/v) for 20 min of sonication showed satisfactory extraction efciency. Recoveries of pesticides from fortied soil samples are over 88% for three different fortication levels between 15 and 200 g kg1 , and relative standard deviations of the recoveries are generally below 6%. Real soil samples were analyzed for OCP residues by optimized ultrasonic solvent extraction and shake-ask as well as soxhlet extraction technique. Investigated all extraction methods showed comparable extraction efciencies. Optimized ultrasonic solvent extraction is the most rapid procedure because the use of time in ultrasonic extraction was considerably reduced compared to shake-ask and soxhlet extraction. 2005 Elsevier B.V. All rights reserved.
Keywords: Soil; Ultrasonic solvent extraction; Organochlorine pesticides; Environmental analysis

1. Introduction The extensive use of pesticides to improve agricultural productivity played an important role in the last century. These compounds have been applied for decades in preventing, repelling or mitigating the effects of pests. Although most of OCP have been banned in many countries because of mutagenic and carcinogenic effects [1], they and their metabolites are still present in the environment, especially in soil and sediment, owing to their persistence and lipophilic properties [2,3]. Therefore, pesticide residue analyses for soil samples continue to be studied more than other environmental contaminant by developing analytical methods, which permit simultaneous determination of environmentally signicant pesticides [4]. At present, more than 60% of registered pesticides and/or their metabolites can be analyzed by using GC, and GC equipped with electron capture detector (ECD) is the most widely used determination technique especially for the OCP analysis [4,5].

Chromatographic analysis usually follows the tedious sample preparation to extract the pollutants from environmental matrices (i.e. soil, sediment, plant material). For the isolation of target compounds from matrices various extraction and cleanup procedures have been proposed. These extraction procedures include, i.e. soxhlet [68], shake-ask [911], sonication [1215], microwave assisted extraction [1619], super critical uid extraction [2024] and pressured liquid extraction [2527]. The preference of each technique mainly depends on solvent and time consumption, ease of operation, etc. Therefore, nowadays, modern methods have been proposed to solve time and solvent consuming problems as an alternative to traditional methods [28]. Although there are various studies, which report that ultrasonic extraction of organic analytes from soil and sediment is very effective [12,14,28], the studies for the application of ultrasonication to extract the OCP from soil are very rare. The aim of this work was to optimize the ultrasonic extraction procedure for the determination of OCP and their metabolites from soil samples. The optimization was carried out with regard to the solvent type, amount of solvent, and duration of sonication. A comparative study on the extraction of OCP residues from real

soil samples was conducted employing the ultrasonic technique, soxhlet extraction and shake-ask methods. 2. Experimental 2.1. Reagents, solvents and adsorbents All chemicals used were of analytical grade. Single pesticide standard, -HCH, -HCH, -HCH, -HCH, heptachlor, aldrin, o,p -DDE, dieldrin, p,p -DDE, p,p -DDT, methoxychlor, mirex, was from Promochem Co. (Wessel, Germany). Solvents used, acetone, n-hexane, ethyl acetate and petroleum ether were from Merck Co. (Darmstat, residue grade). Alumina 90 active, neutral, [(0.0630.200 mm), (70230 mesh ASTM)], were also from Merck Co. (Darmstadt). 2.2. Preparation of spiked samples Soil, which was not treated with any organochlorine pesticides, was collected from a garden in Selcuklu region (Konya). The texture of soil was 56.1% sand, 22.9% silt, 21.0% clay, organic matter: 1.68%, pH (0.01 M CaCl2 ): 7.1 and maximum water capacity: 21.2%. Soil samples were sieved to <2 mm and stored at room temperature until spiking procedure. Spiked soil samples were prepared by adding 200 L of standard mixture of pesticides (the concentration is 10 ng L1 for each compound) to 10 g of soil. This spike level corresponds to 200 g kg1 . Then, 10 mL of acetone was added and suspension was mixed for 30 min with a mechanical shaker. After the bulk of the solvent was evaporated at room temperature, the samples were stored at 4 C in stoppered conical ask for 3 days. Then, the extractions were carried out. 2.3. Calibration range of GC, calibration, limit of detection (LOD) and limit of quantitation (LOQ) For each pesticides determined by GC-ECD, the range of concentrations was appropriated to the levels usually found in environmental samples. In standard solutions used, the concentrations of the compounds ranged between 0.1 and 4 ng L1 , and this range correspond to 10 and 400 g kg1 , respectively. The calibration technique is the external standard multipoint calibration using ve concentration levels (0.1, 0.5, 1.0, 2.0, 4.0 ng L1 ). LOD and LOQ were calculated according to Ref. [29]. Five time analysis of most diluted standard solution (0.1 ng L1 ) was carried out. For each analysis, a standard deviation of signal was obtained and the mean standard deviation was determined. LOD and LOQ were calculated for each analyte by using Eqs. (1) and (2), then converted to unit of g kg1 : LOD = 3S (1/m) LOQ = 3LOD (1) (2)

2.4. Clean-up column Alumina was activated 3 h in an oven at 210 C and then deactivated with 2% H2 O. The clean-up column, length of 30 cm and 10 mm internal diameter, was prepared according to slurrypacking technique [30]. For that, alumina was suspended in nhexane and poured into the column. The column was washed with 50 mL of n-hexane prior to addition of the extract. The extract (1 mL) was transfered top of the column. The elution was carried out with 100 mL of n-hexane:ethylacetate (7/3 v/v) and concentrated to exactly 1 mL using evaporator and nitrogen stream prior to GC-ECD analysis. 2.5. Extraction 2.5.1. Optimization of ultrasonic extraction The recovery experiments were carried out for the determination of efciency of the extraction procedure. At the beginning of the experiments, the extraction efciency of n-hexane, ethyl acetate, acetone and a mixture of petroleum ether and acetone (1/1 v/v) was compared. For that, 10 g of spiked soil was sonicated 20 min with 20 mL of solvents in an ultrasonic bath (frequency 35 kHz, 320 W, Super RK 510, Sonorex, Bandelin, Germany). The extracts were ltered by using Whatman lter paper. The ltrates were reduced to 2 mL with rotary evaporator (Buchi B-160 Vacobox, Switzerland) at 40 C and adjusted to exactly 1 mL with a gentle nitrogen stream. The concentrated extract was transfered onto the clean-up column and elution was performed as described in Section 2.4. The amount of extracted pesticides was determined by GC-ECD and the recoveries (%) were calculated. In the second set of experiments, the optimum volume of solvent, optimum sonication time and optimum repetition of extraction were determined. These optimization experiments were carried out by using of a mixture of petroleum ether and acetone (1/1 v/v), which gave the highest recovery for the pesticides studied. In order to determine optimum volume of petroleum etheracetone mixture (1/1 v/v), 10 g of spiked soil was sonicated for 20 min with 10, 15, 20, 25, 30 and 35 mL of petroleum etheracetone mixture. In order to determine the optimum sonication time, 10 g of spiked soil was sonicated with 25 mL of petroleum etheracetone mixture giving highest recoveries for 10, 15, 20, 25, 30 min. The extraction of 10 g of spiked soil with 25 mL of petroleum etheracetone mixture (1/1 v/v) for 20 min was repeated four times. The cumulative recovery was calculated by adding recoveries of compounds determined in each extract. Three different fortication levels for soil (level 1, 15 g kg1 ; level 2, 45 g kg1 ; level 3, 200 g kg1 ) were performed and fortied samples were stored at 4 C for 3 days and extractions were carried out according to optimum ultrasonic extraction conditions. 2.5.2. Real soil samples Real soil samples were collected from supercial layer (05 cm) of two different commercial orchards (Yunak and Ismil) in Konya. The texture of the soil sample taken from Yunak

where S is the mean standard deviation of ECD signal and m is the slop of the calibration curve.

(Sample A) was 49.2% sand, 32.3% silt, 18.5% clay, organic matter: 1.90%, pH (0.01 M CaCl2 ): 6.5 and maximum water capacity: 19.6%. The texture of the soil sample taken from Ismil (Sample B) was 41.2% sand, 35.0% silt, 23.8% clay, organic matter: 1.36%, pH (0.01 M CaCl2 ): 7.3 and maximum water capacity: 24.1%. Samples were sieved to <2 mm and stored at 4 C until analysis. 2.5.3. Shake-ask extraction Ten grams of real soil sample was suspended in 50 mL of petroleum etheracetone mixture (1/1 v/v) and shaken on a horizontal shaker (GFL Type 3020) for 3 h. The extract was ltered and concentrated to exactly 1 mL by using rotary evaporator and nitrogen stream, respectively. Then clean-up procedure and GCECD analysis were performed as described in Sections 2.4 and 2.5.5, respectively. 2.5.4. Soxhlet extraction Ten grams of real soil sample was weighed into the extraction thimble and extracted with 150 mL of petroleum etheracetone mixture (1/1 v/v) for 4 h. The extract was ltered and concentrated to exactly 1 mL, then clean-up and GC-ECD analyses were performed as described in Sections 2.4 and 2.5.5, respectively. 2.5.5. GC conditions A Hewlett Packard 5890 series II GC, equipped with 6890 series autosampler, 63 Ni-ECD, split-splitless injector and a DB1701 fused silica capillary column (30 m length, 0.25 mm i.d. and 0.25 m lm thickness, J&W Scientic), was used for analysis. Nitrogen was used as carrier (ow rate 1.23 mL/min) and make-up gas (ow rate 42 mL/min). Injector and detector temperatures were 280 and 300 C, respectively, and oven temperature program was 100 C at 20 C/min to 180 C at 4 C/min to 250 C at 15 C/min to 300 C. Two column technique was performed in order to conrm the identity of the OCP. For that, a HP-5 fused silica capillary column (30 m length, 0.25 mm i.d. and 0.25 m lm thickness, J&W Scientic) was additionally used. GC conditions were the same as above. 3. Results and discussion 3.1. Calibration range of GC, LOD, LOQ The calibration curves from ve points for all compounds were plotted by using of peak areas versus injected concentrations. In all cases, correlation coefcients were higher than 0.99. The results for LOD and LOQ are summarized in Table 1. LOD and LOQ values ranged from 1.6 to 3.4 g kg1 and from 4.8 to 10.3 g kg1 , respectively. It was found that LOD values determined are in agreement with the limits given for organochlorine pesticides by Refs. [11,31,32], who studied the determination of organochlorine pesticides using different extraction techniques and GC-ECD.

Table 1 Calibration range, correlation coefcients, LOD and LOQ for organochlorine pesticides studied Pesticide Correlation coefcient 0.999 0.999 1.000 1.000 1.000 0.999 1.000 1.000 1.000 0.999 1.000 1.000 Calibration range (ng L1 ) 0.14.0 0.14.0 0.14.0 0.14.0 0.14.0 0.14.0 0.14.0 0.14.0 0.14.0 0.14.0 0.14.0 0.14.0 LOD (g kg1 ) 3.4 2.7 3.4 2.5 3.0 1.6 3.0 1.8 2.3 2.1 2.5 2.8 LOQ (g kg1 ) 10.2 8.1 10.3 7.5 9.0 4.8 9.1 5.4 6.9 6.3 7.5 8.4

-HCH -HCH -HCH -HCH Heptachlor Aldrin o,p -DDE Dieldrin p,p -DDE p,p -DDT Methoxychlor Mirex

3.2. Clean-up column Environmental extracts contain high proportions of coextracted materials, which may deteriorate the GC analysis. Therefore, these co-extracted substances should be removed prior to quantication by GC. Because the other chemical method, such as oxidation reactions with concentrated sulphuric acid, was destructive for the organochlorine pesticides, adsorption chromatography was preferred for clean up [30]. In order to elute out OCP from the clean-up column, 100 mL of n-hexane:ethylacetate (7/3 v/v) was used and it is investigated whether this amount of solvent is adequate for completely elution of target compounds from clean-up column. For this purpose, 2 g of standard mixture of OCP (2 ng L1 of each compound in 1 mL of n-hexane) was laid onto the column and elution was carried out. The recoveries of target compounds for column chromatography was given in Table 2. It can be clearly seen from Table 2 that 100 mL of nhexane:ethylacetate (7/3 v/v) gives good recoveries for OCP elution. Recoveries and relative standard deviation (R.S.D.) ranged between 92101% and 13%, respectively.
Table 2 The recoveries of OCP for column chromatography (n = 8) Pesticide -HCH, -HCH -HCH -HCH Heptachlor Aldrin o,p -DDE Dieldrin p,p -DDE p,p -DDT Methoxychlor Mirex Recoverya (g) 1.84 1.90 1.96 1.92 1.96 1.94 1.96 1.96 1.98 1.96 2.02 2.00 0.03 0.02 0.02 0.02 0.04 0.04 0.04 0.03 0.02 0.04 0.06 0.04 Recovery (%) 92 95 98 96 98 97 98 98 99 98 101 100 2 1 1 1 2 2 2 2 1 2 3 2

a The recovery was calculated according to the amount of 2 g of standard mixture of OCP.

Table 3 Recovery of pesticides (n = 6) obtained by ultrasonic extraction with various solvents (extracted once, sonication time: 20 min, solvent volume: 20 mL, and fortication level: 200 g kg1 ) n-Hexane Recovery (g kg1 ) -HCH -HCH -HCH -HCH Heptachlor Aldrin o,p -DDE Dieldrin p,p -DDE p,p -DDT Methoxychlor Mirex 98.2 97.5 106.5 111.1 71.1 60.2 106.6 76.9 47.7 44.2 110.4 120.4 4.2 5.0 4.8 6.2 4.3 2.1 5.8 5.7 2.5 2.8 4.6 1.4 Recovery (%) 49 49 53 56 36 30 53 38 24 22 35 60 4 5 5 6 6 3 5 7 5 6 4 1 Ethylacetate Recovery (g kg1 ) 114.6 121.3 115.1 119.7 122.6 123.1 126.9 120.2 120.4 125.3 124.4 124.6 1.5 2.5 1.4 2.4 2.9 2.7 2.7 3.8 1.2 2.6 2.7 2.9 Recovery (%) 57 61 58 60 61 62 63 60 60 63 62 62 1 2 1 2 2 2 2 3 1 2 2 2 Acetone Recovery (g kg1 ) 121.8 127.5 130.8 128.0 128.6 131.3 131.8 129.3 128.3 133.4 130.1 130.6 3.9 5.4 5.0 4.7 3.8 3.0 3.5 4.0 3.7 2.4 3.2 2.6 Recovery (%) 61 64 65 64 64 66 66 65 64 67 65 65 3 4 4 4 3 2 3 3 3 2 2 2 Petroleum ether/acetone (1/1 v/v) Recovery (g kg1 ) 139.5 142.4 149.3 144.7 146.4 150.6 147.1 149.1 142.6 144.7 143.2 140.6 3.1 2.0 3.1 2.3 4.7 5.3 6.0 1.9 3.4 4.6 3.2 2.5 Recovery (%) 70 71 75 72 73 75 74 75 71 72 72 70 2 1 2 2 3 4 4 1 2 3 2 2

3.3. Optimization of ultrasonic solvent extraction procedure The cold liquidsolid extraction is a widely used extraction technique. Years ago the method was began by mechanical shaking and later replaced by ultrasonic treatment. Although there are many data available from literature, which compare sonication with other extraction techniques, for the determination of different pollutants [28,33] such comparisons have not been carried out for OCP extraction from soil. Therefore, the comparison of ultrasonic extraction with other conventional methods, such as shake-ask and soxhlet extraction, for the determination of OCP in soil was also aimed in our study. In the optimization of ultrasonic extraction, different solvents with a wide polarity range like n-hexane, ethylacetate, acetone and a mixture of petroleum ether and acetone (1/1 v/v) were used for sonication. Ultrasonic extraction efciency of the solvents was checked by calculating of recoveries. The results are given in Table 3. The results show that the mixture of petroleum ether and acetone gives the highest recoveries followed by acetone, ethyl acetate and n-hexane in ultrasonic solvent extraction. In soil and sludges, polychlorinated biphenyls (PCB) and OCP are adsorbed on or in soil aggregates. Especially in aged materials it is important to get access to the PCB and OCP adsorbed inside

the aggregates. Acetone, in combination with some mechanical forces, will disintegrate the aggregates, improving the extraction. For these materials acetone in combination with petroleum ether is appropriate [14,34]. That the mixture of petroleum ether and acetone gives the highest recoveries are in agreement with this explanation. Therefore, the mixture of petroleum ether and acetone (1/1 v/v) was used as extraction solvent in further optimization experiments. The aim of the optimization procedure was to improve the extraction efciency with minimum solvent and time consumption during the extraction. Therefore, a careful optimization of the other extraction parameters (i.e. solvent volume, extraction time and number of extraction) would be necessary in order to get satisfactory results. Generally, increasing of the volume of petroleum etheracetone mixture from 10 to 25 mL resulted in increasing of the extraction efciencies for OCP. However, increasing of the volume of solvent mixture from 25 to 35 mL has no affect on the extraction of OCP. Therefore, increasing of petroleum etheracetone mixture volume was stopped and further extraction procedures were carried out by using 25 mL of petroleum etheracetone mixture (1/1 v/v) (see Fig. 1, n = 6).

Fig. 1. Recovery of pesticides as a function of the petroleum ether/acetone (1/1 v/v) volume (extracted once, sonication time: 20 min, (1) -HCH, (2) -HCH, (3) -HCH, (4) -HCH, (5) heptachlor, (6) aldrin, (7) o,p -DDE, (8) dieldrin, (9) p,p -DDE, (10) p,p -DDT, (11) methoxychlor, and (12) mirex).

Fig. 2. Recovery of pesticides as a function of sonication time (extracted once, petroleum ether/acetone (1/1 v/v), volume: 25 mL, (1) -HCH, (2) -HCH, (3) -HCH, (4) -HCH, (5) heptachlor, (6) aldrin, (7) o,p -DDE, (8) dieldrin, (9) p,p -DDE, (10) p,p -DDT, (11) methoxychlor, and (12) mirex).

The authors who studied residue analysis by using ultrasonic extraction often did not indicate sonication time for the optimum extraction [29]. This uncertain point was claried by changing of sonication time from 10 to 30 min. The affect of sonication time on the extraction of OCP can be seen in Fig. 2 (n = 6). It was found that the recoveries increased up to 20 min and there were few uctuations in the recoveries for increasing time from 20 to 30 min. Thus, the optimum sonication time for extraction was selected as 20 min. Because of the fact that the recoveries of pesticides obtained from one step of extraction (25 mL of petroleum etheracetone mixture and 20 min of sonication) ranged from 79% to 91%, extraction should be repeated several times. Therefore, the extraction was carried out four times by adding 25 mL of fresh petroleum etheracetone mixture into the same fortied samples, and cumulative recoveries were calculated by adding recoveries of compounds in each 25 mL of extraction solvent mixture. The compounds were only detected in the extracts from rst and second extraction. However, in the extract from third and fourth extraction step no compounds of interest were detected. Therefore, it was found out that twice ultrasonic extraction should be used in order to obtained satisfactory recoveries for OCP.

Cumulative recoveries ranged from 91% to 101% (see Fig. 3, n = 6). The optimum extraction procedure determined was examined by using of three different fortication levels. The results of recoveries were given in Table 4. According to fortication level 1, recoveries ranged from 92 (4)% to 103 (5)%. Comparable recoveries were also obtained from fortication level 2 and 3 (see Table 4). Statistical signicance among the fortication levels was determined using the two-tailed unpaired Students t-test (at the 95% condence interval) on the quantities of the individual OCP from six replicate analyses of soil samples. In each case, the level of signicance was determined. When statistical evaluation was carried out between quantities of OCP extracted from fortication level 1 and level 2, no significant differences (p > 0.05) were observed. Moreover, the same statistical evaluations were carried out between fortication levels 13 and 23, no signicant differences were observed. This indicated that optimized ultrasonic extraction was of considerable efciency in order to extract OCP from soil samples. A procedural chemical and sample blank were also checked to be sure that interfering compounds were absence. These analyses were carried out using the entire optimized analytical procedure

Table 4 Recovery of OCP (n = 6) for the optimized ultrasonic extraction (twice ultrasonic extraction using 25 mL of petroleum ether:acetone (1:1 v/v) for 20 min of sonication) with three different fortication levels Level 1 (15 g kg1 ) Recovery (g kg1 ) -HCH -HCH -HCH -HCH Heptachlor Aldrin o,p -DDE Dieldrin p,p -DDE p,p -DDT Methoxychlor Mirex 13.8 13.9 14.1 13.9 14.3 14.7 14.8 14.7 14.8 14.9 14.9 15.5 0.6 0.8 0.4 0.6 0.4 0.7 0.7 0.8 0.6 0.5 0.6 0.7 Recovery (%) 92 93 94 93 93 95 99 98 98 99 99 103 4 6 3 4 3 5 5 5 4 3 4 5 Level 2 (45 g kg1 ) Recovery (g kg1 ) 39.8 42.0 42.9 43.0 43.7 43.6 43.8 43.6 44.6 43.9 46.0 45.5 1.3 1.9 0.9 1.4 0.8 1.6 1.1 1.6 1.6 1.4 1.3 1.0 Recovery (%) 88 93 95 96 97 97 97 97 99 98 102 101 3 5 2 3 2 4 3 4 2 3 3 2 Level 3 (200 g kg1 ) Recovery (g kg1 ) 182.0 189.8 191.4 191.4 194.6 198.4 197.4 196.6 199.2 198.0 202.4 204.6 4.0 6.6 3.3 4.8 2.2 5.6 4.3 5.7 4.0 5.3 4.3 3.1 Recovery (%) 91 95 96 96 99 99 97 98 100 99 101 102 2 3 2 3 1 3 1 3 2 3 2 2

Fig. 3. Cumulative recoveries of pesticides as a function of the number of extraction steps (petroleum ether/acetone (1/1 v/v), volume: 25 mL, sonication time: 20 min, (1) -HCH, (2) -HCH, (3) -HCH, (4) -HCH, (5) heptachlor, (6) aldrin, (7) o,p -DDE, (8) dieldrin, (9) p,p -DDE, (10) p,p -DDT, (11) methoxychlor, and (12) mirex).

as well as the same reagents and solvents as for the fortied soils (see Fig. 4). 3.4. Analysis of real soil samples Finally, optimized ultrasonic solvent extraction was compared with shake-ask and soxhlet extraction by means of real sample analysis.

The main disadvantages of the shake-ask and soxhlet extraction methods are that there are needs for more volume of solvent and long time for extraction. Therefore, nowadays automatic devices have been tried to develop to speed up extraction time. The choice of the solvent or solvent mixture is a crucial factor in soxhlet and shake-ask extraction. For aged contaminated soils in which pollutants are present on the surface of particles or, with clayish types of soil, also within clay aggregates, more polar solvent, like acetone in the extraction solvent mixture, is preferred in order to break-up soil aggregates and allow an intensive contact between particles and solvent [34,35]. In our comparison study, the mixture of petroleum ether and acetone (1/1 v/v) was also chosen as extraction solvent for soxhlet and shake-ask extractions. Table 5 shows the results of OCP residues for real soil samples. It can be observed that some of the OCP studied in this work ( -HCH, aldrin, dieldrin, p,p -DDE, methoxychlor and mirex) were detected. As seen in Table 4, ultrasonic solvent extraction gave comparable results with both other extraction procedures. Fig. 5 shows representative chromatograms of soil Sample A. Statistical evaluation indicated no signicant differences (p > 0.05) between the quantities of the OCP residues extracted by ultrasonic solvent extraction and shake-ask extraction. Besides, no statistical differences were determined between the OCP residues extracted by ultrasonic solvent extraction and soxhlet extraction. It should be emphasized that the optimized ultrasonic solvent extraction gives satisfactory results.

Fig. 4. Chromatogram of a spiked soil sample at 15 g kg1 (a), of a sample blank (b) ((1) -HCH, (2) -HCH, (3) -HCH, (4) -HCH, (5) heptachlor, (6) aldrin, (7) o,p -DDE, (8) dieldrin, (9) p,p -DDE, (10) p,p -DDT, (11) methoxychlor, (12) mirex, and column: DB-1701).

Fig. 5. Chromatograms of real soil Sample A: ultrasonic solvent extraction (a), shake-ask extraction (b), and soxhlet extraction (c) ((6) aldrin, (8) dieldrin, (12) mirex, and column DB-1701).

Table 5 Comparison of ultrasonic extraction, shake-ask extraction and soxhlet extraction for OCP residue levels in real soil samples Concentration (g kg1 ) (n = 10) Soil A Ultrasonic extractiona -HCH -HCH -HCH -HCH Heptachlor Aldrin o,p -DDE Dieldrin p,p -DDE p,p -DDT Methoxychlor Mirex
a b

Soil B Shake-ask extraction nd nd nd nd nd 12.7 1.5 nd 17.3 0.4 nd nd nd 19.4 3.2 Soxhlet extraction nd nd nd nd nd 13.2 0.6 nd 18.2 0.8 nd nd nd 20.9 1.1 Ultrasonic extractiona nd nd nd 22.5 0.6 nd 44.8 2.1 nd nd 27.4 1.2 nd 35.8 2.7 nd Shake-ask extraction nd nd nd 21.9 2.5 nd 41.8 4.2 nd nd 25.9 2.6 nd 32.1 5.2 nd Soxhlet extraction nd nd nd 23.3 1.3 nd 42.5 3.6 nd nd 28.2 1.7 nd 37.2 1.9 nd

ndb nd nd nd nd 13.5 0.3 nd 17.6 0.5 nd nd nd 21.4 0.5

Twice ultrasonic extraction using 25 mL of petroleum etheracetone mixture for 20 min of sonication. Not detected.

Table 6 Retention times of OCP for DB-1701 and HP-5 fused silica capillary column Retention times (min) DB-1701 -HCH -HCH -HCH -HCH Heptachlor Aldrin o,p -DDE Dieldrin p,p -DDE p,p -DDT Methoxychlor Mirex 11.22 12.66 13.37 14.41 15.53 16.52 17.80 19.97 22.53 23.09 24.53 24.85 HP-5 10.09 10.82 11.06 11.80 13.54 14.85 17.58 19.04 20.67 22.26 24.13 25.40

Solvent consumption is an important parameter above all for economical reasons. For the extraction techniques of ultrasonic and shake-ask, much lower volumes of organic solvents were needed compared to soxhlet extraction. Reconcentration and clean-up steps have to be performed for all extraction techniques. 4. Conclusion The results obtained indicated that the ultrasonic solvent extraction method could be efciently applied in order to extract OCP from soils. Recoveries of pesticides from fortied soil samples are over 92%, 88% and 91% for fortication level 1, 2 and 3, respectively, with the relative standard deviations generally below 6%. The ultrasonic solvent extraction is more rapid than conventional shake-ask and soxhlet extraction methods. The solvent consumption is also signicantly lower than other method applied. By using of ultrasonic solvent extraction, the time consumption was reduced approximately 75% and 82% compared to shake-ask and soxhlet extraction used in our study, respectively. Solvent reduction is near to 67% compared to soxhlet extraction. Acknowledgement The authors thank Dr. Sait Gezgin, who is the lecturer in Agricultural Faculty of Selcuk University (Konya), for his help during the soil texture analyses. References
[1] G.R. van der Hoff, P. van Zoonen, J. Chromatogr. A 843 (1999) 301. [2] T.A.T. Aboul-Kassim, B.R.T. Simoneit, Interaction Mechanisms between Organic Pollutants and Solid Phase Systems. Handbook of Environmental Chemistry, Springer Verlag Publisher, Heidelberg, Berlin, 2001, p. 4.

The conrmation of residue identity of the studied OCP was performed by two column technique. For this purpose, in addition to DB-1701, a HP-5 fused silica capillary column was used. The retention times of OCP for DB-1701 and HP-5 columns in GC condition described in Section 2.5.5 were presented in Table 6. A comparison of general parameters of the extraction methods is shown in Table 7. The extraction time for the sonication was very short compared to soxhlet extraction. The shake-ask extraction time was between ultrasonic and soxhlet extraction.
Table 7 Comparison of general parameters for the different extraction techniques used General parameters Extraction time (h) Solvent volume (mL) Reconcentration step Need for clean up Cost Ultrasonic 0.7 50 Yes Yes Low Shake-ask 3 50 Yes Yes Medium Soxhlet 4 150 Yes Yes Medium

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